DE1745904A1 - Means for influencing plant growth and processes for the production of its active ingredients - Google Patents

Description

GERMAN GOLD ■ UIiD SILVER-SCHEIDEANSTALT FORMERLY ROESSLBR Frankfurt am Main, Volsafrauen · trasae 9

With toi for influencing do · plant growth and process for the production of its active components

The invention relates to new compounds, methods for their preparation and their use as influencing agents

deo Pflajütsenwachsturns, especially as Hörbi Bide.

It is now known that 2, 4 ~ Bi8-alkyla «lno-6 <-azldo ~ 1 , 3» 5-triazines are used to influence plant growth

The new compounds of the present invention correspond to the general formula

Js

N..1 J

In this Foreel, X mean an -OR-ι <SR "or -CN- group

or a halogen atom, preferably chlorine atom, R a lower one

1 2 alkyl group with 1 to k carbon atoms and R and R are the same

or different and mean hydrogen, lower alkyl or alkenyl groups, optionally s «B. by -OR-, -CN "or N0_ groups can be substituted

The new compounds are able to influence the growth of plants even in low concentrations. When used in suitable quantities, they can be used as herbicides

009816/1877

Connections of the claimed kind can be Jo according to the kind

1 2 the subatituenton R, R, R and X to eradication or

selective suppression of weeds among crops or also serve to completely kill and prevent undesired vegetation. UU they könnon for influencing dos plants Guard Turns be used, for example, "to defoliation, reducing the Fruohtaneatzo9 _r delay flowering etc ₀ Likewise wio to influence the laudatory plant, these Vorbindungen" are also used to sterilize the soil, you can either alone or in a mixture can be used with each other or together with other horbizlden substances · They can also be used with insecticides or fungicides or with fertilizers ml so hen c

Examples of suitable solvents for the triazine compounds are alcohols, ketones, hydrocarbons, such as toluene, halogenated hydrocarbons, such as chloronaphthalene, mineral oils, such as diesel oil "vegetable oil" or "r Mixtures of the substances mentioned «

The claimed Triazlnverbindungen can in known Types that are familiar to every Faohmann on this goblet are used, whereby the selection of the application kind of the given circumstances and dsn property · * d ·· Herbicide ·· depends. In general one needs biersu di known formulations.

0 098 16/1877 bad original

You can use ZrBo in more or less concentrated solutions produce organic Loungesittel} the nan before use veitor n diluted with these solvents ο

The solutions in solvents "let old water be available." five LPnon »it water was constricted. Here they fall Triczine pre-bindingon in solid or flüaaicwr fora from ο these iiueponßicnnn odor Eiaulaionon can by known substances stabilized: been

Han can also supply the triaesin preconditions on foe tan carriers to * uondoii. All such Itonuaon are known for this purpose, ZoB "Toil; Kaolin, Kiesolgiir _? Bantonit, Talcua, finely ground calcimaoarbonat, charcoal , wood flour and the like ₀

The active ingredient © can be _{combined with the carrier materials in a dry fora 0} Han can also spray solutions or emulsions onto the carrier materials or scorch them with them and then dry the oil mixture ^

To toffe better adhesion of the kneading) on the carriers ssu orroichen _E can be known adhesives like glue "casein, alginic acid ₁ Sal2fe and similar materials used ο

One can schlieselich the triazo, optionally zusnmfflon bit don carriers, cause narrow with Suspensionsaittoln and stabilizers, Z ₀ B. processed into a paste or Onea Pulvor, and then with water Diose su a suspension anrührenr

0098 1 6/1877

Wetting agents, emulsifiers and stabilizers ktfnnen anionic kationieobe or not lonogone known Stoffο be used SoB _n TUrklschrotöl, salts of fatty acids, Alkylaryloulfonato, eokundäre sulfates _t harzeauro salts Polyttthylonäther Pott alcohols, fatty acids or Pettaminen _t quartrtro ammonium compounds · Lignlnsu] fosflure _t saponin , Gelatin, casein for one or more times with one another

Dio neuon pre-bindings can be made; if SrD _{n is} a pre-bond of the general formula

Hal II

In dor Hal a halogen, preferably chlorine, let, at a temperature of about 20 to about 50 ° C with a salt, preferably an alkali salt, of hydrazoic acid in the presence of water and / or an organic solvent to form a compound of the general formula

BATH

' ^Γ 009816/1877

174590 *

Aluminum organic solvents can include ketones, Ether, Ea tor, DiwethyljTorejanjid, especially Alkoiiole or duren Loouagan * bztr * Hiaohuugon, vert / OAdet been »The U» · JLu Suoponeion can also be carried out «

: ':; i its ^. obanfalle iiiögllph ,. olno connection of general

.-'- JVEl'ji

Shark

j; i JS to iv

in 'Im- Y means a Saueratoff- odor sulfur atom, in' ■ Jrti.jtJijvrart from auwindoot katrtlytlnchon Ho? i £ sn cineo _t üogcb.in the case of a mixed aliphatic tertiary amine * yorsugBweise trlniothylamine, and in the presence of an organic Iiüsim Preferably an alcohol, optionally in the normal way with water as the solvent, at a temperature of about 20 to about 50 ° C. with a salt, preferably alkali, of hydrogen hydrogen acid to form a compound of the general formula

to implement. The amine can be up to equimolecular in the reaction Quantities are available. Usually it goes from 0.01 to

009816/1877

Oi6 MuI Amiη per mole of Trlazlnverblundung au », among the Loans agree that methanol is preferred "

One can also use a compound dor allgoaelnon formula IV in Ougonwurt oinoo Inorten org & nlonhen Ltfoungeialttele with / iqiiimol ocular on amounts of oinoa lower, optionally gomisohten, "aliphatic tertiary AmX aa, before auge white trimethylamine "endo compound, the quaternary aluminum product" do and then in the presence of uaetsoi * urid / or einoa /, alcohol or dimethyl, foriuamid boi diner temperature of otic, 20 to 50 ° C with a SaIa, vovzu ^ ovfelso an alkaline, the nitrogen fwaufloretoffeäuro from a compound of the allgomelnon Fornel In addition, in dioexn cases, Bsneol, Oenzln and Kohlonwae nor stoff can be used as inert solubilizing agents. Wolter let go possible, a preliminary binding of the general formula IV in a polar organic solvent before isugaweise in dimethylformanide or N-methylpyrrolidone at one temperature from about 50 to about 100 ° C with a salt, preferably an alkali salt, nitrogen Hydrogen acid su a compound of the general formula V urneοtson »'

You can also use a compound of the general formula

»3

Hal VI

0098 16/1877 bad original

With an alcohol at a temperature between about 20 * C and the boiling point of the organic solvent used, preferably the alcohols of the alcoholates to a compound of the general formula

OR VII

realize"

Finally, it was found that Ban _f a compound of the general formula VI as described above, in the presence of at least catalytic amounts or at least equimolar amounts of a tertiary amine using an alkali metal cyanides _r preferably Natriumoyanid, a salt of hydrazoic acid in place to form a compound of the general formula VII can implement o

The compound .VI can also be in a polar organic solvent, preferably in dimethylformamide or N-methylpyrrolidone at a temperature of about 50 to about 100 ° C with an alkali as hydrogen cyanide »preferably with sodium cyanide» to a compound of the general formula

CN VIII

are reacted _t where in the formulas II to VIII R _f R and R are those according to the formula I ang. 009816/1877

R, R ″ and R have the meaning given according to formula I.

8AD ORIGINAL

•

Example It 2-Xeopropylaaino <»4-azidO" 6-ohlor <-e-tria8in

92.25 ff (■ 0.5 mol) Cyanurolalorid are in 250 ■! Acetone exchanged and cooled to 0 ° C. At this temperature, 43 g of 70% aqueous isopropylamine solution and 100 μl of 20% sodium hydroxide solution are run in while stirring. Care should be taken that the pH of the mixture does not exceed 8. Anaehlloaend are given a suspension τοη 34.1 g sodium aside in 50 ml H ₂ O hiaxra and let the temperature rise to 35 to ko * C · After 6 hours du.J Aoeton is stripped off in vacuo and the crystalline residue is sucked off and chlorine-free gowasoheno

After drying in vacuo, there remain € 99 white crystals with a melting point of 70 to 71 * C.

Analyzes

C ^ H ₈ N ₇ Cl calcd C 33.7 * »H 3β76 N 45.86 Cl 16.6

(M - 213.5) found 33 91 3 9 46.1 16 5

The yield is £ 92.8 of theory.

Using the same method, the following subetansons were produced 1

- ο "

0098 16/1877

ßAD

R ¹ R ² 112 Fp • c H CH - 113 • c H 79 60 • c H Yes O k9 - 80 • c H Ju ^ * Q 79 - 50 * C CH ₃ CH ₃ - 80 C ₂ H ₅ C ₂ H ₅ oao oil C (charred) H H 210

Be i »piol 21

-e -triamine

1? 75 e sodium lust nan In 100 ml of methanol and add anaohlieoeond 15 ff 2-ethylamino ^ -azido-6-chloro-e-triasjin o Han boils for about 30 minutes under reflux, until the solution roagiert neutral _e Daa methanol is now in the The vacuum is removed and the back stand »it Vaseer is set. Sr crystallizes quickly and becomes abutable »

After drying, 10 * 75 g of a white powder remain from melting point 100 to 101 * C.

Analysis

C ₆ H ₉ N ₇ O calcd. C 36.9 H k "6 N 50.25 (M m 195) found 37 * 1 ^ 7 *" 9 "9

Exploits 73 <> 3 % of theory ο

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009816/1877

Using the same method, the following sub-tons were also used manufactured!

"j"

R. R ¹ R ² Fp CH ₃ H C ₃ H ^ i 110-111 * C CH ₃ H C ₄ H ₉ t oil CH ₃ H CH ₃ 113-116 · C CH ₃ H H above 250 * C (Ze: CH ₃ C ₂ H ₅ C ₂ H ₅ oil C ₂ H ₅ C ₂ H ₅ ⁰ A oil

Example 31 2-Ioopropylamlno ~ lt-azido-6-BOthylaeroapto-a-trlasine

21 g of 2-l0opropylamlno ~ 4 ~ chloro ~ 6 ~ methylmeroaptotriasln are dissolved in 100 μl of methanol, and a solution of 6.9 g of sodium aside in kO al water is added. About 6 g of trinetylaninOas are now passed in. The temperature rises to 53 ° C. The mixture is then stirred for a further 2 hours at this temperature. The methanol is evaporated off in vacuo and the residue is taken up in water. Sr soon crystallizes through and is sucked off. After drying, 20.2 g one g "lblioh ~ white powder with a Sohmel point 85 to 86 ° C. remains.

009816/1877

BATH ORIGINAL

Analyeet

C ₇ H _n N ₇ S calculates C 37 * H 4.9 M h $, 6 S

225)

found

37 »7

3 · 1

43.6 "

13 * 9

Exploits 89 * 5 # of the theory

Analogously, the following compounds are hergc were represents t

N,

R. R ¹ R ² Fp ο CH ₃ H CH ₃ 159-160 · C CH ₃ H C ₂ H ₅ 110-112 · C CH ₃ H c ^ -t hk - 46 · C CH ₃ . H C ₅ H _{1 r} t oil CH ₃ CHj CH ₃ I4i - 1 * 2 * C C ₄ H ₉ -n H C ₂ H ₅ 71-73 * C H C ^ -i 39-40C H c ^ -t oil C ₂ H ₅ oil

- 12 -

009816/1877

⁶⁴⁰

Belepiol k ι 2 ~ methylamino ~ Zl-aBido ~ 6-oyanotriaBln

25 β 2 "Nethylamino-t» - »a8ldo ~ 6-ohlortri aisin loot into 250 ml of methanol and add 3.3 g of sodium cyanide, which had been added to 20 ml of H ₂ O» Now, at 0 bl 10 g of triethylamine gas at 5 ° C., then stirred for 2 hours at 20 ° C. and the methanol evaporated in vacuo. The residue is taken up with water, filtered off with suction and dried in vacuo. A light yellow powder melting points is obtained 119 ble 120 * C. Menget 13.2 g.

Analysis ι calculated C. 3 «» .1 H 2. 3 N 63 = 6 ^C 3 ^H i » ^H 8 found 33 • 9 2. 5 62 .9 (M - 176)

2 ~ t-Butylamino-4-aeido ~ 6-oyano-s-triaEin (yellow Ul) and 2-Xeopropylamlno »*» - azido-6 <-oyano ~ e »triasin (Pp · 119 to 120 * C) produced ·

Some examples of typical forms of application follow Example St

10 parts of 2-Xeopropylamlno-i »-aBidO" 6-ohlor-s-trlasln, 89 parts of bentonite or kieselguhr and 1 part of a hoohdlspersen, pyrogenic silica are ground in a ball mill with a fine fineness Daa Gemlsoh is used as a dusting agent

- 13 -

009816/1877

i.4V;: ■■ - ■ r - ι BAD ORIGINAL

-.L ₁ -? Iol 6 ι

t olno Liisuii. ^ of 20 parts of 2-t butylamino h · - ■ · »: ϋ'Γ / 6-ttGtho3ty · ο - fcriaiiin. 5 ¹ O · parts of dimethylformamide and 10 '...}}. Xon oinos Alkylury.lpolyelykolätharOo This preparation "ic ι' / ^ ifc v / asoor mixed vordon and are stable Oino

Mi · * ».vi ■> .LXt elno iliocliunf- Hör, consisting of 25 Toilon 2-l« Propyl aj-.rj ■ it-asldo-6 «wöfcliyl! R; oroapto-e-triaaln _I 50 Toilon Methyl = cyJ.iitjo.-imon, 15 Toilon xylene and 10 parts of a subetitu ior- oii Wapiithalinauli'oaHuro consists ₀ The misehiing results in mi- -iiiBuor oina otnbilo dispersion.

B «i.3niol 81

20 foilo 2 "XthyliiHino '> ^ - azido ~ 6 cyano ^ a-triaain, 70 parts Kaolin, 7 parts olnea Schwofoloäureeotore ainos Alkylpoly » glycolüthorn and 3 Toilo Calcivusi ^ Lignin ^ Sulphonate Folnut vorahlenc Dao Pulvor can be suspended and can be used anywhere uses werdon «

At opiel ^ ₁ »

To prevent the herbicidal activity of the new compounds, the experiments described below are not used

1 ο Soil treatment after sowing t

In a Gtlaahaue kept at 21 ° C, various Seeds in soil that was in plastic bowls, oinge « rakes, watered with Vassor in the morning and in the afternoon Treated with a dispersion that by Singiessen a

009816/1877 BATH ORIGINAL

Solution doa Wirketoffee in the same ΤοΛΙβ Waesor orhalton Then at noriaalor Bow & seerung dda Spriooaen the Plants observed and sswsi Vochon romps after the Auaaaat featgea whether and in what way: Maaae dor Pflansonwuohs was suppressed vrordon ·

2 “Bodonbohandlung after Sprioesens

In a glassworks kept at 21 * C it has been versohiedone Seeds οingoharkt in soil. After dom Soriouaen was the one above he * saluted wäoariffe Oieperslon dea Virkatoffes on the ground auigobrüohto Two Vochon later it was fcctgoateilt whether and the vigilance was reduced to a great extent.

3ο Blattbohandlung according to dom Sprleaaeni

Ea was just as with Z " vorfahren, only old de" differentiated, that the wüosrigo Dioperaion deo '/ Irkatoffes was applied to the soil, but to the leaves of the plant.

The results of the Versuoho are in the table below contain »The numbers mean the amount of deodorant active ingredient» auegodrliokt in kg per ha »which is necessary to do 50% · Destroy Plant Wuohses "

a) Investigated connections of the general Porael

- Cl

- 13 -

009816/1877

Compound A; Z ■ -NHCH ₃ compound Bs Z * -NHC ₂ H ₅ compound CsZ- -NHC ₃ H ₇ -I compound DsZ * -NHBut-t

S May "> oats

oo

_ * Lolch o (lollum ^ perenne) co peas ^ flax

sugar beet

Soil treatment the seed after Ein _f D. ; Soil treatment B. after to the , 9 ^D. Leaf treatment after B. C. D. «3 bring B. > 10 Sprout 20th 0 I.
> 20 Sprout > 10 > 10 7th o2 A. > 10 C. ? 10 A. 20th C. > 20
I. A. 5.2 3.6 1 > 10 4.9 Mon :> 20> 8.5 > 20 £ '10 4.2 ^<1 .4 > 10 3 60 3 > 10 > 20> 20th 3 ° 5 ί * 10 6.2 5.0 2 2.3 > 10 2.8 > 20 6.6 5. ⁰ ^ 1 oO ^ 10 3.4 <1 <1 MO 8.3 > 10 <1 > 20> 6.2 > 20 <1.0 ^ 10 1.0 <1 <1 > 10 2.4 2c 8th O 20th 1OcO <1 <1cO 9o1 •egg <1 8o9 6.8 <1 2 Io < 1 > 10 7 ^ 8 < 1

cn co ο

b) Investigates · compounds of the general formula

Z-C.

May a

oats

Lolch (lolit perenae)

peas

Flax

mustard

Sugar raven

Connection A * R Compound Bs R Compound C: R Connection D? R. Connection E: R

CH CH

-NHC ₂ H ₅

3 '" CH ₃ ; Z

CH ₃ ; C ₄ H ₉₅

-NHC ₃ H ₇ -I -NHCH _n

Soil treatment after sowing the seeds

1.2

1.7 3.1 2.2

■ 1.5

2.9

MO

/ 10

/ 10

Soil treatment after sprouting

> 20> 20

> 20 2 6

7-8

> 20> 20> 20

> 20

12 -> 20> 20

> 20

16.3 3 0

> 20 £ 1 0 2 3 <1ο0

> 20> 20> 20

> 20

Leaf treatment after sprouting

IcO

7th

7.0 U6

7-0 1.-6 2.0

<1eO

1.9

6.7

2.0 <1oO

<1 <1oO

MO

3

-CD

ι? -

J:;. L- »Λ Ol

With οίηαη ötUuboraittoI aue 10 Tollen 2-1 Propyl & Mlno " Kötho ^ y-s-fcriaaln and 90 Tollen Talkiua pollinated young Loineaat pflanaon zaigtan 2 days according to dor Behaudlting £ 3 heavy foliage

1 1 ί

i? l «a Cuopynaiou a Miochunä of 20 tolls 2 t Du ty I amino- ύ-> αζ ± ύθ" ό-νγ: Μύ -a ■ triazine, l? 0 Toilon Dimethylfo? * »a: ait2 and 10 tolls, ,!., -. ylaryl ^ olyglykolJithor in Wasuer mrdo auf Junge Sonfpflanztm aui ' so spray t _r ίίκΛη 2 Tu ^ -η η were i.5L »ao vollkoawen

- 18 "

009816/1877

Claims (1)

1, means for Booinfluoeung dee Pflanaonwacheturne, characterized in that daaa βο ale virkeamea Boat and to 11 mindee icons a connection dor allgouolnen Formol en thill t * in this formula, X means an -OR-, "SR- = odor ■ CN group or a halo tone, vorssugoweioa Chlorates", R let oine lower alkyl groups with 1 to k C atoms, R and R ^{2 one} and the same or vorechieden and mean tfaeeeretoff "lower alkyl- odor alkonyl group, which can be given" full, zoBt by -Uli-, "üK- or wö ₂ 'groupeu, eubatltuiort aein ₀ 2ο Procedure for dividing up a real existing avenue Means according to claim 1, characterized in “daee man ontweder α) a compound of the general formula Shark II in the shark a halogen ", presumably chlorates", let, at a temperature of about 20 to about 50 * C old one Salt, presumably an alkali alm, "he nitrogen waaeer- 009816/1877 bad original ■ α ftoffoäuro in the presence of a vase; he and / or an organic Löeiuiecisit'iolo to elnor prior to binding the Fortsol III ztf odor
b) oino compound of the general formula Shark .1 YR IV V ΠΙ * N ..a ι - in which Y denotes an oxygen or sulfur atom, in the presence of also catalytic hens a lower, given case, aliphatic tertiary arylamine _F, preferably trimethylamine, and in the presence of an organic solvent, an alcohol, optionally mixed with water , as a solvent at a temperature of about 20 to about 50 ° C with a salt _r, preferably an alkali, the nitrogenous acid to a compound of the general formula urneetat ₉ odor «20 009816/1877 BATH ORIGINAL ο) a compound dor general formula IV converts in the presence of an internal organism Ltieuncsinittole with ttquinole kularon Hongon oinoa lower, gogcbonon, mixed, aliphatic terfcifiron amine, preferably trimethylamine, then isolated in the presence of a quaternary compound forming a quaternary compound by Vae & er and / or ο ine β All -eise! s οή + r Dime thy 1formamide with a teii perature from otna 20 to οIw d) a compound dor general formula IV in a polar organic Lönun ^ oraittol _f vorsugewoiae in Dirnethylfonaamid or N-methylpyrrolidone at a temperature of about 50 to about 100 * C with a Sal "preferably Alkaliealz _r of SticketofftraesorotoffeUure to a compound of general formol V implements, odor e) a compound dor the general formula VI with an alcohol at a temperature between about 20 * C and the boiling point of the organic solvent used, preferably the alcohols of the alcohol tea au a compound of the general formula VII implements, odor 009816/1877 OFHG1N ^AL 17A5904 ·; ') Ülii.-i compound of the general formula VI nil · an alkali « ο y an id ,, voi'zuvoloo sodium anide, according to one of the methods described under b) _r c) and d) to a compound of the allgomoinon Fortaol N - C ί - CN VIII 1 umsotat, woboi in Poraels II to VIII R, R and R have the meaning given in claim 1 16. ^. 196 Dr.No/Ha 8AD ORIGINAL 009816/1877